Ethylenimino-s-triazines



Patented Sept. 29,

5,653,934 ErnYLfiNii'iiINo-s-mmzmEs I Donaldfiaiser gld Greenwich, and Frederic C; Scha'efcr, Stamford; Qoiu'n; assifinors" to American Cyanamid Company,- New York," N. Y.,"' a corporation of Maine l lo Drawing. ruitt-",; I i050, Serl 6 Claims. (01. tat-545.6)

. Th present m eer ii are bis-ethylenimino-s-triazines oi the general formula:

mo' oii; N

inwhich R1 is a member otthegroupconsisting of hydrogen, halogen, aliphatic, aromatic; amino, and alkylamino'; and Rd is a member oi the group consisting of R1 and ethylenimino.

Compounds of the. above class are 118811111120 pharmaceutical preparations, resins, and' in textile treatment.

The compounds of the present" invention can be made by reacting ethyle'nimine with the corresponding s-tria'zin'yl halide. The reaction fs'a general one and can be" carried out in aqueous solution with an inorganic alkaline a'ci-d'acceptor such as sodium hydroxide or the'lik'e. A'nalternate procedure is to use benzene as"; the" solvent and an organic base, such'as' triethylaminefas the acid acceptor. I I I With the exception of dichloro-"s tria'ziriej'the starting halo triazinyl compounds" canbe" made by methods well known in the artgg'ehemw irom cyanuric chloride, such as by the methodsdisclosed by Klason, J. prakt. Chem; 2, 345152-60 (1886), Diels et a 1., Ber. 36', 319'l-"7" (1903), and Ostrogovich, Chem. Ztg. 36,73'8-9 (1012 The following examples illustrate without limiting the invention.

EXAMPLE 1 Preparation of monoethylener'neldmln rapt 73.0 g. (0.5 mole) 2,4-diamin'o 6-chldio-s tflazine.

20.0 g. (0.5 mole) sodiumhydroxide."

21.5 g. (0.5 mole) ethylenimine? 800 cc. water.

abovere'agents are heated. rapidly to Cg w'ith stirring. The mixture is held at this temperature for 20minutes, filtered hot, and the insoluble material is washed withcold, water. The 62 gp oi' crude product so obtained is added to I500 cc.- 0'1" boiling water. and dissolved by vigorous mixing for about .1- -2 minutes. The solution is filtered and the filtrate is cooled rapidly. The solute crystalli'z'esslowl'y at 10 C. The crystalline product weighed 2 5 .6 g. M. P. 220-225 c.

EXAMPDE 2 Preparation 51' 2-ethylrtimino-4,6-dimethomy-striazine A solution of 12.9 g. (0.30 mole) of ethylene mine and 33.3 g. (0.33 mole) of triethylamine in cc. of benzene wasadded during 35 minutes to a mixture of 33.9 g (0.15. mole) of 2,4-dichloro-6-phenyl-s-triazine' and 80 cc. of benzene while the reaction mixture was held at 15-20 C. When the addition was complete the mixture was warmed at 35-C.]ior one hour and then at 50 C. for thirty minutes. The'benzene solution 3 was then filtered from the insoluble trlethylamine hydrochloride. By partial evaporation of the benzene solution 14.5 g. of crystalline product was obtained. This was recrystallized from 80 cc. benzene plus 50 cc. of heptane, giving 10.9 g., M. P. 142 C. (dec.).

EXAMPLE 4 Preparation of diethyline melamine To a slurry of 165 g. (1.0 mole) oi 2-amino-4,6- dlchloro-s-triazine and 1 liter of water stirred at 25 C. is added a solution of 86.0 g. (2.0 moles) of ethylenimine and 88.0 g. (2.2 moles) of sodium hydroxide in 1 liter of water. The reaction mixture is stirred for one hour at C. after the Preparation of Z-chloro-4,6-bisethyZenimino-striazine A solution of 46.1 g. (0.25 mole) of cyanuric chloride in 100 cc. of dioxane was run into 500 cc. of stirred, ice-cold water to produce a finely divided suspension of the cyanuric chloride. To this at 1:11" C. was added in 25 minutes a solution of 22.0 g. (0.51 mole) of ethylenimine and 69.1 g. (0.50 mole) of potassium carbonate in 500 cc. of water. As the addition progressed the mixture became quite thick. It was stirred 10 minutes longer at 1 C. and then was filtered. The pasty product was washed with water and dried at 60 C. in a forced draft oven. The dry product weighed 34.5 g. This crude material was extracted with a mixture of 300 cc. of carbon tetrachloride and 200 cc. of chloroform. From the solution was recovered 23.5 g., M. P. 132-135 C. dec., (47% yield of recrystallized product). Further recrystallization from benzene yielded material melting with decomposition at 135 C.

EXAMPLE 6 Preparation of 2,4-bisethylenimino-fi-methoxy-striazine ()OHa (if CH1 om CH5 CH2 To a mixture of 36.0 g. of 2,4-dichloro-6- methoxy-s-triazine and 80 cc. of benzene, is added 4 at 10-20 C. a solution of 17.2 g. (0.40 mole) of ethylenimine and 44.4 g. (0.44 mole) of triethylamine in cc. of benzene. Reaction is strongly exothermic and the addition takes about 30 minutes. The mixture is then warmed at 35-38 C. for 90 minutes. It is filtered and the filter cake washed with a little benzene. The benzene filtrate and washings are evaporated at reduced pressure 30 C.) to a partly crystalline residue. The crystals are filtered and washed with benzene. After air drying the product weighs 15.5 g., M. P. 112 C. Material recrystallized from a mixture of benzene and heptane melts at 114- 116C.

EXAMPLE 7 Preparation of 2,4-bz's(ethylenimino)-striazine A. A 0.40 mole batch of aqueous ethylenimine was prepared by heating the following mixture at 50 C. for 80 minutes.

46.4 g. (0.400 mole) 2-chloroethylamine hydrochloride.

280 cc. water.

32.0 g. (0.40 mole) sodium hydroxide.

42.4 g. (0.40 mole) sodium carbonate.

(The reagents were mixed in the order listed.)

B. The ethylenimine solution was cooled to 3 C., and during 40 minutes a solution of 30.0 g. (.20 mole) of 2,4-dichloro-s-triazine in 100 cc. of acetonitrile was added at 34 C. The cooling bath was then removed and the mixture was allowed to warm naturally to 19 C. in 80 minutes. The insoluble salts (mainly sodium bicarbonate) were filtered out and washed with a little cold water and with chloroform. The combined filtrate and washings were extracted with 300 cc. of chloroform in four portions, and the chloroform solution was evaporated to dryness. The crystalline residue was taken up in approximately 100 cc. of warm benzene, the solution was filtered, and the solute was recrystallized by cooling. The crystals were washed with benzene and dried in a forced draft oven at 70 C. The dry product weighed 11.0 g. and melted at about 120 C. with decomposition. The mother liquor was concen trated and an additional 8.4 g. of lower melting material recovered. Thus the total yield of crude 2,4-bis(ethylenimino) -s-triazine was 59%.

Recrystallization of the 11.0 g. fraction from '75 cc. of benzene yielded 6.5 g., M. P. 147w C. dec.

The 2,4-dichloro-s-triazine used in Example '7 was made in the following way:

A mixture of 2 equivalents of cyanogen chloride and 1 equivalent of hydrogen cyanide was heated with 0.10 equivalent of hydrogen chloride as a catalyst at 60 C. for 12 hours. The thus-formed 2,4-dichloro-s-triazine is recovered by distilling off the unreacted reagents, dissolving the residue in benzene, filtering from insolubles and distilling the benzene extract. The compound distills at 100-102 C./75 mm. and solidifies. The compound melts at 52-54 C. and can be recrystallized from hexane.

While the invention has been described with particular reference to specific embodiments, it is to be understood that it is not to be limited thereto but is to be construed broadly and restricted solely by the scope of the appended claims.

5 We claim: 1. A compound of the formula H70\T/CH2 1 5 N/ \N Rg- F-Rx 10 in which R1 is a, member of the group consisting of hydrogen, halogen, alkoxy, aromatic hydrocarbon, and amino, and R2 is a member of the group consisting of R1 and ethylenimino.

Number GIOIRW 2,4-bis(ethy1enimino) -s-triazine.

DONALD W. KAISER. FREDERIC C. SCHAEFE'R.

References Cited in the file of this patent UNITED STATES PATENTS Name Date Wystrach et a1. Aug. 29, 1950 2,4-bis (ethylenimino) -6-methoxy-s-triazine. 

1. A COMPOUND OF THE FORMULA 